CN107507958A - A kind of powder in situ cladding for lithium-sulfur cell prepares integral method with pole plate - Google Patents
A kind of powder in situ cladding for lithium-sulfur cell prepares integral method with pole plate Download PDFInfo
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Abstract
The present invention relates to a kind of powder in situ cladding for lithium-sulfur cell to prepare integral method with pole plate, and this method includes：After organic solvent is mixed with water, it is 8.5 with ammoniacal liquor regulation pH value, obtains mixed liquor；Positive active material, Dopamine hydrochloride are dispersed in gained mixed liquor and obtain suspension；Ammonia is fully volatilized the heating of gained suspension, add conductive agent, anode sizing agent is made in binding agent；By anode sizing agent coated on plus plate current-collecting body, positive plate is drying to obtain.The preparation method realizes positive electrode powder cladding and being made into one of pole piece, shortens technological process and manufacturing cycle, reduces production cost；Dopamine issues in weakly alkaline environment is born from polymerisation formation poly-dopamine, and positive active material is coated using its good film forming, improves the cyclical stability of lithium-sulfur cell；Technological process is simple, and production efficiency is high, is adapted to large-scale industrial production.
Description
Technical field
The invention belongs to lithium-sulfur cell technical field, and in particular to a kind of for the powder in situ cladding of lithium-sulfur cell and pole
Plate prepares integral method.
Background technology
With society and economic fast development, also change with rapid changepl. never-ending changes and improvements is occurring for our life.Portable use
Electrical equipment, electrical source of power gradually come into our life, and these electronic products cause high-energy-density energy storage to set for the demand of the energy
The standby ever more important that seems.Lithium ion battery as a kind of new secondary cell, be acknowledged as the energy-storage system be most potential it
One.But because current commercialized lithium ion battery is more relatively low than energy, price is high, does not meet the need of people
Ask.Therefore, developing the energy storage device that energy of future generation is high, price is low, long lifespan, safety are secure turns into widely studied in the recent period
Focus.
Lithium-sulfur cell, be using elemental sulfur as positive pole, lithium metal as negative pole serondary lithium battery.Lithium-sulfur cell have with
Under it is particularly significant the characteristics of：1) sulphur as active material is widely present in the earth's crust, therefore sulphur simple substance is cheap；2) sulphur is made
For active material when, its theoretical specific capacity is up to 1675mAh/g, and theory is 2600Wh/Kg than energy, equivalent to city at present
3-5 times of the secondary cell of fieldization；3) relative commercial lithium ion battery, lithium-sulfur cell environmental pollution are smaller.Nevertheless,
Because it has the disadvantage that, lithium-sulfur cell is not able to extensive use.First, the insulating properties of elemental sulfur：At ambient temperature,
The conductance of elemental sulfur is 5 × 10-30S/cm, so being insulator, therefore it is unfavorable for the electric conductivity of electrode；Second, polysulfide ion
Dissolve and migrate in the electrolytic solution：Lithium-sulfur cell is multistep reaction in the charge and discharge process of battery, is deposited in electrochemical process
In many intermediate products, these intermediate products can be dissolved among electrolyte and be migrated to negative pole direction, that is, so-called
" shuttle effect ", the problems such as so as to cause battery capacity to reduce；3rd, the expansion of sulphur volume in electrochemical reaction：In electrochemistry
Among reaction, there is larger volumetric expansion in sulphur, and these Volume Changes can cause expendable damage to electrode structure.
For these problems, many scholars have put into great efforts and have achieved prominent achievement.For improving elemental sulfur
Poorly conductive, scholars build conductive network using conductive carbon, so as to play the purpose for improving electrode conductivuty.For " wearing
Shuttle effect ", people fetter the migration of polysulfide ion using the strong adsorptivity of micropore using having micropore/meso-porous carbon material.Pin
To volumetric expansion problem, people reasonably carry sulfur content or accommodated with flexible electrode using optimizing porous carbon/sulphur composite
Gentle solution volumetric expansion brings stress damage to electrode structure.In addition to carbon material, polymer also progresses into researcher's
The visual field.Application of the polymer among lithium ion battery can be largely classified into modification of the polymer to battery lead plate, polymer to every
The modification of film, cladding of the polymer to powder body material.As Chinese patent CN102723491B discloses a kind of conducting polymer
Lithium-ion battery composite-electrode material of cladding and preparation method thereof is impregnated, using the method polymer of dipping to powder body material
Coated, then prepare electrode, the material capacity crossed by polymer overmold is greatly improved.And for example Chinese patent
CN102280656A discloses a kind of preparation method of the lithium ion battery of positive electrode covered by conductive polymer, adds lead in the slurry
Electric polymer or conducting polymer monomer are coated so that battery capacity is than improving 10-20% before uncoated.The above method
The cyclical stability of lithium ion battery is improved to a certain extent, or improves the capacity of battery, but building-up process ratio
It is more complicated cumbersome.
In the prior art, CN104795544A discloses a kind of lithium sulfur battery anode material, by hollow nano-sulfur ball and gathers
Dopamine film forms, and poly-dopamine film is coated on the surface of hollow nano-sulfur ball.Its preparation method is to be dissolved in dispersant
In ionized water, sulphur source is added, is uniformly dispersed, dropwise reaction acid, reacted 4-24h, separated after centrifugation, cleaned, dry, obtain hollow
Nano-sulfur ball；The hollow nano-sulfur ball is added in buffer solution and is uniformly dispersed, dopamine hydrochloride solid is added, under ultrasound
Polymerisation 4-24h is carried out, is separated after centrifugation, is cleaned, dries, obtains the lithium sulfur battery anode material.CN104617327A
A kind of lithium sulfur battery anode material is disclosed, the positive electrode center is functionalized carbon nano material, and intermediate course is sulphur, outside
Layer is poly-dopamine film, and the functionalized carbon nano material is hydroxylating carbon nanomaterial or carboxylated carbon nanomaterial.It is made
Preparation Method is that carbon nanomaterial is dissolved in into acquisition functionalized carbon nano material in alkali or acid solution；Functionalized carbon nano material is added
Enter in the sulphur source aqueous solution, diluted acid is added dropwise after stirring, obtain the functionalized carbon nano material of outside cladding sulphur；By outside cladding sulphur
Functionalized carbon nano material is added in three (methylol) aminomethane buffers with dopamine hydrochloride solution polymerization, is obtained described
Positive electrode.Above-mentioned technical proposal is first to prepare the positive electrode powder of poly-dopamine film cladding, then by positive electrode powder
Slurry is made, then prepares pole piece, process complexity is cumbersome, long preparation period, low production efficiency, and cost is high.
The content of the invention
It is an object of the invention to provide a kind of powder in situ cladding for lithium-sulfur cell to prepare integral method with pole plate,
Technological process is simple, short preparation period, and production efficiency is high, and cost is low.
In order to realize the above object the technical solution adopted in the present invention is：
A kind of powder in situ cladding for lithium-sulfur cell prepares integral method with pole plate, comprises the following steps：
1) after organic solvent is mixed with water, it is 8.5 with the pH value of ammoniacal liquor regulation system, obtains mixed liquor；
2) positive active material, Dopamine hydrochloride are dispersed in mixed liquor obtained by step 1), obtain suspension；
3) suspension obtained by step 2) is heated after ammonia is fully volatilized, adds conductive agent, positive pole slurry is made in binding agent
Material；
4) anode sizing agent obtained by step 3) is drying to obtain positive plate coated on plus plate current-collecting body.
The powder in situ cladding for lithium-sulfur cell of the present invention prepares integral method with pole plate, from Dopamine hydrochloride
As covering, under mild alkaline conditions, auto polymerization reaction is brought it about, using the good continuous film forming of poly-dopamine, is aligned
Pole active material is coated；Binding agent and conductive agent are added in suspension, slurry is prepared into after being sufficiently stirred, then directly
Pole plate is prepared, so as to realize that it is integrated that powder cladding is prepared with pole plate.
Traditional technique is by lithium-sulfur cell active material under certain specified conditions, with conducting polymer or work(
Energy fluidized polymer is coated to it, and then the material after cladding is centrifuged or filtered, obtains polymer overmold powder
Body material；Or cushioning liquid is adjusted into pH value of solution, then powder body material is coated；After cladding, filter, do
Composite after being coated after dry；Afterwards brushing piece is being carried out according to the pole plate manufacture craft of classics.Classical powder bag
Coating process complexity is cumbersome, flow burden, and power consumption is high and low yield, so that can extend manufacture cycle unavoidably and increase production
Cost, it is unfavorable for commercially producing.
In the preparation process in accordance with the present invention, by the use of ammoniacal liquor as pH adjusting agent, weak base condition is provided for the polymerization of dopamine, so
Afterwards by heating, ammoniacal liquor is volatilized, aqueous binders are then added according to the quality of sulphur in suspension, directly prepare pole plate, work
Skill flow is simple, short preparation period, and production efficiency is high, and cost is low, is advantageously used for commercial production.
In step 1), the organic solvent is any one or combination in absolute ethyl alcohol, ethylene glycol, isopropanol, acetone.
When organic solvent is the mixture of above-mentioned many kinds of substance, many kinds of substance can be arbitrary proportion.
In step 1), the volume ratio of organic solvent and water is 1:(0.5~3).Wherein, water used is preferably deionization
Water.
For step 1) in regulation system pH, under stirring, ammoniacal liquor is added dropwise to system dropwise.
In step 2), the positive active material is any one or combination in elemental sulfur, carbon/sulphur composite.Institute
Stating carbon/sulphur composite can be multiple for CNT/sulphur composite, hollow carbon sphere/sulphur composite, hollow carbon fiber/sulphur
Any one or more in condensation material.The content of sulphur is the 20~80% of gross mass in the carbon/sulphur composite.
In step 2), the quality of Dopamine hydrochloride for Dopamine hydrochloride and positive active material quality sum 0.5%~
6%.
It is described to be separated into ultrasonic disperse in step 2).In the step, the concentration of positive active material is controllable to 0.05~
5g/mL。
In step 3), the heating refers to that carrying out forced air drying to suspension makes the ammonia in system fully volatilize.Will be outstanding
Turbid is placed in air dry oven, ammonia is fully volatilized.
In step 3), the temperature of the heating is 70~90 DEG C.
Conductive agent, the dosage of binding agent are：The mass ratio of positive active material and conductive agent, binding agent is 7:2:1.
The conductive agent is any one or combination in Super P, conductive carbon black, Ketjen black.
The binding agent is aqueous binders.Preferably, the binding agent is beta-schardinger dextrin, polyethylene glycol oxide, methylol
Any one in cellulose, sodium alginate or combination.
The plus plate current-collecting body is aluminium foil.
The powder in situ cladding for lithium-sulfur cell of the present invention prepares integral method with pole plate, the cladding work with routine
Skill contrasts, and the preparation flow, as pH adjusting agent, substitutes traditional cushioning liquid, by whole system from lower-cost ammoniacal liquor
It is adjusted to be advantageous to the mild alkaline conditions of dopamine polymerization, provides for the polymerization of dopamine and suitable obtain capsulation condition；The preparation method
Positive electrode powder cladding and pole piece (pole plate) being made into one are realized, so as to shorten technological process and manufacturing cycle, is reduced
Production cost；Auto polymerization can occur under weakly alkaline environment and react to form poly-dopamine for dopamine, good using poly-dopamine
Film forming positive active material is coated, so as to improve the cyclical stability of lithium-sulfur cell；The preparation method technique stream
Journey is simple, short preparation period, and production efficiency is high, and raw material sources are extensively and cheap, and cost is low, substantially pollution-free to environment, is adapted to
Large-scale industrial production.
A kind of positive plate as obtained by above-mentioned preparation method.
A kind of lithium-sulfur cell, including positive pole, negative pole, barrier film and electrolyte, the positive pole use above-mentioned positive plate.
The positive plate of the present invention can improve the cyclical stability of lithium-sulfur cell, improve lithium-sulfur cell capacity and decline as positive pole
Subtract the problem of fast.
Negative material used in the negative pole is lithium metal or lithium alloy；The lithium alloy is Li/Si alloys, Li/Sn conjunctions
Gold, or Li/C alloys.The electrolyte is the solution that electrolyte lithium salt is formed in nonaqueous solvents.Wherein, electrolyte lithium salt is
Lithium perchlorate (LiClO4), lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), double (fluoroform sulphonyl) imine lithiums
(LiTFSI) any one or more in.The concentration of electrolyte lithium salt is 0.8~1.2mol/L.Nonaqueous solvents is ethylene carbonate
Any one or more in ester (EC), dimethyl carbonate (DMC), 1,3- dioxolanes (DOL), glycol dimethyl ether (DME).
Also contain lithium nitrate in the electrolyte as additive, the concentration of lithium nitrate is 0.1mol/L.The barrier film is the secondary electricity of lithium
The conventional lithium ion battery separator in pond field.The lithium-sulfur cell for making to form using the positive superfine product of above-mentioned material and the present invention has more
Good chemical property.
The lithium-sulfur cell of the present invention, there is stable cycle performance, higher specific capacity, in 0.150mA/cm2Charge and discharge
Under electric current density, first discharge specific capacity is not less than 825mAh/g, and specific discharge capacity remains at after 100 circulations
706mAh/g, and testing result is reproducible, moves towards market for high-energy-density secondary cell of future generation and has established solid foundation.
Brief description of the drawings
Fig. 1 is that the powder in situ cladding for lithium-sulfur cell of the present invention prepares the flow chart of integral method with pole plate；
Fig. 2 is that the cross section FESEM of the gained S@PDA-2 pole pieces of embodiment 1 schemes；
Fig. 3 is the EDS elementary analysis figures of the cross section of the gained S@PDA-2 pole pieces of embodiment 1；
Fig. 4 is circulation-capacity phenogram of embodiment 1-3 and the lithium-sulfur cell of comparative example 1；
Fig. 5 is circulation-capacity phenogram of the lithium-sulfur cell of embodiment 4 and comparative example 2.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Embodiment 1
The powder in situ cladding that the present embodiment is used for lithium-sulfur cell prepares integral method (flow chart such as Fig. 1 institutes with pole plate
Show), comprise the following steps：
1) it is 1 according to the volume ratio of absolute ethyl alcohol and deionized water:2 ratio, absolute ethyl alcohol is mixed with water；Stirring bar
Under part, ammoniacal liquor is added dropwise in above-mentioned system dropwise, the pH value of regulation system is 8.5 (being detected with pH meter), obtains mixed liquor；
2) taking elemental sulfur (positive active material) to add in mixed liquor obtained by step 1), (concentration for making elemental sulfur is 0.1g/
Ml), ultrasonic 30min makes its dispersed；Then it is 98 according to the mass ratio of elemental sulfur and Dopamine hydrochloride:2 ratio, add
Dopamine hydrochloride, 2h is persistently stirred, obtain suspension；
3) suspension obtained by step 2) is placed in forced air drying 30min in 80 DEG C of air dry ovens, ammonia is fully volatilized；
Conductive agent, binding agent are added into system, 4h is sufficiently stirred, becomes pasty state, anode sizing agent is made；
Wherein, the conductive agent is SP, and the binding agent is polyethylene glycol oxide (PEO), beta-schardinger dextrin, carboxymethyl cellulose
Sodium (CMC) three mass ratio is 3:2:1 mixture；The mass ratio of elemental sulfur and conductive agent, binding agent is 7:2:1；
4) by anode sizing agent Direct Uniform obtained by step 3) coated in (the load sulfur content of unit area on plus plate current-collecting body aluminium foil
For 1mg/cm2), produce positive plate after 60 DEG C of vacuum drying.
It is S@PDA-2 pole pieces by positive plate obtained by the present embodiment, a diameter of 12mm disk is cut on slitter, is treated
With.
The cross section FESEM of S@PDA-2 pole pieces is schemed as shown in Fig. 2 EDS elementary analyses figure such as Fig. 3 institutes obtained by the present embodiment
Show.Sulphur, nitrogen are can be seen that from Fig. 2, Fig. 3, oxygen element is uniformly distributed, and shows that the sulfur granules in pole piece are uniformly coated by dopamine.
The lithium-sulfur cell of the present embodiment is assembled in water, oxygen content is both less than in 0.1ppm argon atmosphere glove box and carried out.
Using above-mentioned gained S PDA pole pieces as positive pole, metal lithium sheet is assembled into CR2016 type buttons as negative pole with barrier film, electrolyte
Battery.Wherein, the electrolyte lithium salt in electrolyte is double trifluoromethanesulfonimide lithiums (LiTFSI), concentration 1mol/L；It is non-
Aqueous solvent is that the volume ratio of both glycol dimethyl ether (DME) and 1,3- dioxolanes (DOL) is 2:1 mixed solvent；Also contain
There is the lithium nitrate that concentration is 0.1mol/L as additive.
Embodiment 2
The powder in situ cladding that the present embodiment is used for lithium-sulfur cell prepares integral method with pole plate, comprises the following steps：
1) it is 1 according to the volume ratio of absolute ethyl alcohol and deionized water:2 ratio, absolute ethyl alcohol is mixed with water；Stirring bar
Under part, ammoniacal liquor is added dropwise in above-mentioned system dropwise, the pH value of regulation system is 8.5 (being detected with pH meter), obtains mixed liquor；
2) taking elemental sulfur (positive active material) to add in mixed liquor obtained by step 1), (concentration for making elemental sulfur is 0.1g/
Ml), ultrasonic 30min makes its dispersed；Then it is 96 according to the mass ratio of elemental sulfur and Dopamine hydrochloride:4 ratio, add
Dopamine hydrochloride, 2h is persistently stirred, obtain suspension；
3) suspension obtained by step 2) is placed in forced air drying 30min in 80 DEG C of air dry ovens, ammonia is fully volatilized；
Conductive agent, binding agent are added into system, 4h is sufficiently stirred, becomes pasty state, anode sizing agent is made；
Wherein, the conductive agent is SP, and the binding agent is polyethylene glycol oxide (PEO), beta-schardinger dextrin, carboxymethyl cellulose
Sodium (CMC) three mass ratio is 3:2:1 mixture；The mass ratio of elemental sulfur and conductive agent, binding agent is 7:2:1；
4) by anode sizing agent Direct Uniform obtained by step 3) coated in (the load sulfur content of unit area on plus plate current-collecting body aluminium foil
For 1mg/cm2), produce positive plate after 60 DEG C of vacuum drying.
It is S@PDA-4 pole pieces by positive plate obtained by the present embodiment, a diameter of 12mm disk is cut on slitter, is treated
With.
The lithium-sulfur cell of the present embodiment, using above-mentioned gained S@PDA-4 pole pieces, remaining is the same as embodiment 1 for positive pole.
Embodiment 3
The powder in situ cladding that the present embodiment is used for lithium-sulfur cell prepares integral method with pole plate, comprises the following steps：
1) it is 1 according to the volume ratio of absolute ethyl alcohol and deionized water:2 ratio, absolute ethyl alcohol is mixed with water；Stirring bar
Under part, ammoniacal liquor is added dropwise in above-mentioned system dropwise, the pH value of regulation system is 8.5 (being detected with pH meter), obtains mixed liquor；
2) taking elemental sulfur (positive active material) to add in mixed liquor obtained by step 1), (concentration for making elemental sulfur is 0.1g/
Ml), ultrasonic 30min makes its dispersed；Then it is 94 according to the mass ratio of elemental sulfur and Dopamine hydrochloride:6 ratio, add
Dopamine hydrochloride, 2h is persistently stirred, obtain suspension；
3) suspension obtained by step 2) is placed in forced air drying 30min in 80 DEG C of air dry ovens, ammonia is fully volatilized；
Conductive agent, binding agent are added into system, 4h is sufficiently stirred, becomes pasty state, anode sizing agent is made；
Wherein, the conductive agent is SP, and the binding agent is polyethylene glycol oxide (PEO), beta-schardinger dextrin, carboxymethyl cellulose
Sodium (CMC) three mass ratio is 3:2:1 mixture；The mass ratio of elemental sulfur and conductive agent, binding agent is 7:2:1；
4) by anode sizing agent Direct Uniform obtained by step 3), coated in plus plate current-collecting body aluminium foil, (the load sulfur content of unit area is
1mg/cm2) on, produce positive plate after 60 DEG C of vacuum drying.
It is S@PDA-6 pole pieces by positive plate obtained by the present embodiment, a diameter of 12mm disk is cut on slitter, is treated
With.
The lithium-sulfur cell of the present embodiment, using above-mentioned gained S@PDA-6 pole pieces, remaining is the same as embodiment 1 for positive pole.
Embodiment 4
The powder in situ cladding that the present embodiment is used for lithium-sulfur cell prepares integral method with pole plate, comprises the following steps：
1) it is 1 according to the volume ratio of isopropanol and deionized water:2 ratio, isopropanol is mixed with water；Stirring condition
Under, ammoniacal liquor is added dropwise in above-mentioned system dropwise, the pH value of regulation system is 8.5 (being detected with pH meter), obtains mixed liquor；
2) hollow carbon fiber/sulphur composite (ACF/S, composite in sulfur content 50%) is taken to add mixed obtained by step 1)
Close in liquid (concentration of composite is 0.15g/ml), ultrasonic 30min makes its dispersed；Then according to Dopamine hydrochloride and again
The mass ratio of condensation material is 6:100 ratio, Dopamine hydrochloride is added, 2h is persistently stirred, obtains suspension；
3) suspension obtained by step 2) is placed in forced air drying 30min in 80 DEG C of air dry ovens, ammonia is fully volatilized；
Conductive agent, binding agent are added into system, 4h is sufficiently stirred, becomes pasty state, anode sizing agent is made；
Wherein, the conductive agent is SP, and the binding agent is sodium alginate；Hollow carbon fiber/sulphur composite and conduction
Agent, the mass ratio of binding agent are 7:2:1；
4) by anode sizing agent Direct Uniform obtained by step 3), coated in plus plate current-collecting body aluminium foil, (the load sulfur content of unit area is
1mg/cm2) on, produce positive plate after 60 DEG C of vacuum drying.
It is ACF/S@PDA pole pieces by positive plate obtained by the present embodiment, a diameter of 12mm disk is cut on slitter,
It is stand-by.
The lithium-sulfur cell of the present embodiment is assembled in water, oxygen content is both less than in 0.1ppm argon atmosphere glove box and carried out.
Using above-mentioned gained ACF/S PDA pole pieces as positive pole, metal lithium sheet is assembled into CR2016 types as negative pole with barrier film, electrolyte
Button cell.Wherein, the electrolyte lithium salt in electrolyte is double trifluoromethanesulfonimide lithiums (LiTFSI), concentration 1mol/
L；Nonaqueous solvents is that the volume ratio of both glycol dimethyl ether (DME) and 1,3- dioxolanes (DOL) is 2:1 mixed solvent；
Also contain concentration be 0.1mol/L lithium nitrate as additive.
Comparative example 1
The positive plate of this comparative example, in preparation process, directly by elemental sulfur and conductive agent carbon black (SP), aqueous binders
(mass ratio of polyethylene glycol oxide, beta-schardinger dextrin and sodium carboxymethylcellulose is 3:2:1 mixture) in mass ratio 7:2:1 is mixed
Close, using deionized water as solvent, be uniformly applied to after sizing mixing in current collector aluminum foil, then 60 DEG C of vacuum drying 6h, tabletting, are prepared into
Lithium-sulphur cell positive electrode piece.
In glove box, with the above-mentioned positive plate positive pole prepared, with negative pole, barrier film, electrolyte, be assembled into button electricity
Pond, specifically with embodiment 1.
Comparative example 2
The positive plate of this comparative example, in preparation process, directly by hollow carbon fiber/sulphur composite (ACF/S) with leading
Electric agent carbon black (SP), sodium alginate in mass ratio 7:2:1 mixing, using deionized water as solvent, is uniformly applied to collector after sizing mixing
On aluminium foil, then 60 DEG C of vacuum drying 6h, tabletting, are prepared into lithium-sulphur cell positive electrode piece.
In glove box, with the above-mentioned positive plate positive pole prepared, with negative pole, barrier film, electrolyte, be assembled into button electricity
Pond, specifically with embodiment 4.
Experimental example
This experimental example carries out electrical property using LADN test systems to embodiment 1-4 and comparative example 1-2 lithium-sulfur cell
Test.Wherein, charging and discharging currents density is 0.150mA/cm2, discharge and recharge blanking voltage is：1.6-2.8V(vs.Li/Li+).On
The specific discharge capacity for stating lithium-sulfur cell see the table below 1 and Fig. 4, Fig. 5.
The electric performance test result of table 1
| Object | Initial discharge specific capacity (mAh/g) | Specific discharge capacity after circulating 100 times |
| Embodiment 1 | 731 | 640 |
| Embodiment 2 | 825 | 706 |
| Embodiment 3 | 684 | 614 |
| Embodiment 4 | 1074 | 643 |
| Comparative example 1 | 375 | 280 |
| Comparative example 2 | 1054 | 561 |
It is can be seen that from table 1 and Fig. 4, Fig. 5 by comparative example and lithium-sulfur cell chemical property phase obtained by each embodiment
Than using the lithium-sulfur cell of positive plate obtained by the preparation method of the present invention, specific capacity, cyclical stability are improved largely.
Test result indicates that the powder in situ cladding for lithium-sulfur cell of the invention prepares integral method, gained positive pole with pole plate
Piece can effectively suppress the dissolving of polysulfide in the electrolytic solution in charge and discharge process, reduce polysulfide to lithium anode
Corrosion, so as to improve the cyclical stability of lithium-sulfur cell.In addition, the production cycle is greatly shortened in the technique, reduction is produced into
This, to realize that lithium-sulfur cell industrialized production is laid a good foundation.
Claims (8)
1. a kind of powder in situ cladding for lithium-sulfur cell prepares integral method with pole plate, it is characterised in that：Including following
Step：
1) after organic solvent is mixed with water, it is 8.5 with the pH value of ammoniacal liquor regulation system, obtains mixed liquor；
2) positive active material, Dopamine hydrochloride are dispersed in mixed liquor obtained by step 1), obtain suspension；
3) suspension obtained by step 2) is heated after ammonia is fully volatilized, adds conductive agent, anode sizing agent is made in binding agent；
4) anode sizing agent obtained by step 3) is drying to obtain positive plate coated on plus plate current-collecting body.
2. the powder in situ cladding according to claim 1 for lithium-sulfur cell prepares integral method with pole plate, it is special
Sign is：In step 1), the organic solvent is any one or combination in absolute ethyl alcohol, ethylene glycol, isopropanol, acetone.
3. the powder in situ cladding according to claim 1 or 2 for lithium-sulfur cell prepares integral method with pole plate, its
It is characterised by：In step 1), the volume ratio of organic solvent and water is 1:(0.5~3).
4. the powder in situ cladding according to claim 1 for lithium-sulfur cell prepares integral method with pole plate, it is special
Sign is：In step 2), the positive active material is any one or combination in elemental sulfur, carbon/sulphur composite.
5. the powder in situ cladding for lithium-sulfur cell according to claim 1 or 4 prepares integral method with pole plate, its
It is characterised by：In step 2), the quality of Dopamine hydrochloride for Dopamine hydrochloride and positive active material quality sum 0.5%~
6%.
6. the powder in situ cladding according to claim 1 for lithium-sulfur cell prepares integral method with pole plate, it is special
Sign is：In step 3), the heating refers to that carrying out forced air drying to suspension makes the ammonia in system fully volatilize.
7. the powder in situ cladding according to claim 1 for lithium-sulfur cell prepares integral method with pole plate, it is special
Sign is：Conductive agent, the dosage of binding agent are：The mass ratio of positive active material and conductive agent, binding agent is 7:2:1.
8. the powder in situ cladding for lithium-sulfur cell according to claim 1 or 7 prepares integral method with pole plate, its
It is characterised by：The conductive agent is any one or combination in Super P, conductive carbon black, Ketjen black；The binding agent be β-
Any one in cyclodextrin, polyethylene glycol oxide, hydroxymethyl cellulose, sodium alginate or combination.
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